CN110368914A - A kind of composite water treatment medicament and preparation method thereof for heavy metal containing wastewater treatment - Google Patents
A kind of composite water treatment medicament and preparation method thereof for heavy metal containing wastewater treatment Download PDFInfo
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- CN110368914A CN110368914A CN201910595595.2A CN201910595595A CN110368914A CN 110368914 A CN110368914 A CN 110368914A CN 201910595595 A CN201910595595 A CN 201910595595A CN 110368914 A CN110368914 A CN 110368914A
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0225—Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
- B01J20/0229—Compounds of Fe
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0274—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04 characterised by the type of anion
- B01J20/0281—Sulfates of compounds other than those provided for in B01J20/045
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0274—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04 characterised by the type of anion
- B01J20/0288—Halides of compounds other than those provided for in B01J20/046
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/14—Diatomaceous earth
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
Abstract
The invention discloses a kind of composite water treatment medicament for heavy metal containing wastewater treatment, constituents are as follows: polyglutamic acid, starch, FeCl3·6H2O、FeSO4·7H2O, sodium metasilicate, humic acid, diatomite magnesium stearate, sugarcane waste residue, polyethylene glycol, tributyl phosphate.Preparation method are as follows: (one) MODIFIED Fe3O4Particle preparation: by polyethylene glycol and FeCl3·6H2O、FeSO4·7H2O carries out reaction preparation MODIFIED Fe3O4Particle；(2) preparation of magnetic composite microsphere: taking polyglutamic acid, starch sodium metasilicate to be placed in reaction kettle, under sodium hydroxide, initiator, crosslinking action with MODIFIED Fe3O4Particle is compound to prepare magnetic composite microsphere；(3) it will be mixed after diatomite, sugarcane waste residue progress high-temperature activation with magnetic composite microsphere, activator mixture material, humic acid, obtain composite water treatment medicament under magnesium stearate, tributyl phosphate, coupling agent, dispersing agent effect.
Description
Technical field
The invention belongs to technical field of heavy metal wastewater treatment, and in particular to a kind of for the compound of heavy metal containing wastewater treatment
Water treatment agent and preparation method thereof.
Background technique
In recent years, with the quick raising of rapid development of economy and industry, there is great progress in society, but people simultaneously
Class is also faced with increasingly severe environmental problem, and current main environmental problem is exactly the pollution of heavy metal.Heavy metal cannot
Be biodegradable, on the contrary can the hundreds of enrichment in the food chain of biology, can finally enter human body, in human body and albumen
The strong interaction of the generations such as matter and enzyme, causes them slowly to inactivate, it is also possible to it is enriched in certain organs in human body,
Slow poisoning is caused, human health is seriously endangered.The source of heavy metal and quantity be increasing and water quality increasingly
Complexity also results in increasingly severe threat to the health of natural environment and the mankind.Therefore, the processing of heavy metal is had become
The problem of being concerned.
Since there are many industry for forming heavy metal contaminants, so the source of heavy metal is extremely wide, mainly have: 1. industrial
Pollution sources are such as electroplated, steel, mining, machining, non-ferrous metal metallurgy and the discharge of part chemical company exhaust gas, useless
Water, waste residue, waste material etc.；2. the unreasonable use of agricultural pollution source such as chemical fertilizer and pesticide and carrying out the untreated of field irrigation
Sewage etc.；3. the heavy metal ion of refuse battery in domestic pollution source such as rubbish, waste electric appliance dissolution；4. transportation source mainly comes
From the abrasion of gold-plated part, the burning of gasoline engine oil and the discharge of vehicle exhaust of automobile engine and tire.Heavy metal
Pollution course has the characteristics that wide source, non-biodegradable and cumulative bad.
The constituent of heavy metal wastewater thereby is complicated, therefore processing technique is also diversified.It proposes both at home and abroad very much
Processing method is broadly divided into chemical method, physical method and bioanalysis.1. chemical method.Chemical precipitation method is due to easy to operate, economical
The features such as economical, is widely used in industrial processes at most effective, most traditional method for removing removing heavy metals.It is former
Reason is to chemically react it with the heavy metal in waste water, by waste water by the way that other chemical substances such as alkali or flocculant is added
The heavy metal ion of middle dissolved state is changed into insoluble heavy metal compound, removes precipitation and separation in waste water after filtering
Heavy metal ion.Chemical precipitation method includes neutralization precipitation method, sulphide precipitation, ferrite coprecipitation etc. again.At chemical method
It is relatively easy to manage heavy metal wastewater thereby technique, but after handling be difficult that waste water is made to reach discharge standard, need to be for further processing, and handles
The heavy metal pollution amount generated afterwards is big, Yi Fanrong, easily causes secondary pollution.2. physical method.Physical method is not changed in heavy metal
Become under chemical form, heavy metal ion is collected to the method for being concentrated and then separating.Wherein absorption method is using adsorbent to a huge sum of money
Belong to the method that physics, chemistry or the microbe adherence trait of ion remove removing heavy metals.Usually in the treatment of waste water, absorption refers to several
Adsorb coefficient result.Adsorbent has a various advantage and disadvantage, the type of adsorbent be also it is various, it is active
Charcoal, zeolite, molecular sieve, there are also adsorb resinae etc..Physical method primary attachment method, ion-exchange, membrane separation process etc..Absorption method
Heavy metal wastewater thereby is handled, easy to operate, efficient, adsorbent species multiplicity, is the heavy metal containing wastewater treatment side being most widely used
Method.However, most widely used adsorbent is active carbon now, although it has stronger adsorption capacity, to heavy metal ion
Removal rate is high, but its regeneration efficiency is low, and which limits its large-scale applications industrially.3. bioanalysis.Bioanalysis is benefit
A kind of method for reaching purification of waste water with biological metabolic product and heavy metal ion interaction, has environmental benefit good and cost
Low advantage.Bio-flocculation process, biosorption process, phytoremediation etc. can be divided into.Bioanalysis since application conditions are harsher,
It is not easy to control, rest on theoretical research stage more.Currently, there are many medicament of heavy metal containing wastewater treatment field of purification both at home and abroad, place
Reason medicament property is unstable, and treatment agent dosage is big, and treatment effect is undesirable, and actual motion operation is comparatively laborious.
Summary of the invention
It is an object of the invention to, processing unstable for treatment agent property present in existing heavy metal containing wastewater treatment
The problems such as dosing is big, and treatment effect is undesirable, provide a kind of composite water treatment medicament for heavy metal containing wastewater treatment and
Preparation method, the treatment agent property that the present invention is prepared is stable, dosage is few, high treating effect, easy to use.
The scheme of the invention is realize in this way:
A kind of composite water treatment medicament for heavy metal containing wastewater treatment, each constituent of composite water treatment medicament raw material
And its weight fraction ratio are as follows: 25~30 parts of polyglutamic acids, 22~30 parts of starch, 12~18 parts of FeCl3·6H2O, 12~18 parts
FeSO4·7H2O, 20~26 parts of sodium metasilicate, 18~20 parts of humic acid, 12~16 parts of diatomite, 8~10 parts of magnesium stearates, 10~
16 parts of sugarcane waste residues, 30~35 parts of polyethylene glycol, 8~12 parts of tributyl phosphates.
As a further explanation of the present invention, the polyethylene glycol is polyethylene glycol 200, polyethylene glycol 400, poly- second two
The combination of one or more of alcohol 1000, polyethylene glycol 1500.
A method of preparing the composite water treatment medicament for heavy metal containing wastewater treatment, comprising the following steps:
Step 1) MODIFIED Fe3O4Particle preparation: 12~18 parts of FeCl are taken3·6H2O, 12~18 parts of FeSO4·7H2O dissolution
In 25~40 parts of distilled water, 6~8min is stirred under conditions of stirring rate is 30~40r/min, is then added 30~35
Part polyethylene glycol, the under nitrogen protection prepared 2molL of fast drop-1NaOH solution adjusts pH to 9, is then in temperature
Water bath with thermostatic control 60min cools the temperature to room temperature under the conditions of 60 DEG C and mixing speed are 800~850r/min, with magnet by reactant
It answers product to precipitate, is washed repeatedly several times with distilled water and dehydrated alcohol, 5~6h is dried in vacuo at 40~50 DEG C and is modified
Fe3O4Particle；
Step 2) magnetic composite microsphere preparation: take 25~30 parts of polyglutamic acids, 22~30 parts of starch, 20~26 parts of silicon
Sour sodium is placed in reaction kettle, then be added 50~60 parts of distilled water stirring rate be 60~80r/min under the conditions of stirring 4~
6min adds 12~14 parts of sodium hydroxides, 5~8 parts of initiators, 6~8 parts of crosslinking agents and is stirred equal and rear addition step 1
Obtained MODIFIED Fe3O4Particle reacts 4~4.5h under the conditions of temperature is 120~130 DEG C and stirring rate is 60~80r/min
Afterwards, then with water, dehydrated alcohol it successively washs, filter, divided after constant weight is finally dried under vacuum under the conditions of 50~60 DEG C with magnet
From, collect and obtain magnetic composite microsphere；
Step 3) composite water treatment medicament preparation: take 12~16 parts of diatomite, 10~16 parts of sugarcane waste residues mix
It is even to be placed in high temperature furnace, 60~90min of activation is carried out at 300~500 DEG C, setting warming temperature is set as 6 DEG C/min, then
Activator mixture material is taken out to be cooled to room temperature；The magnetic composite microsphere and activator mixture after cooling for taking step 2 to be prepared
Material, 18~20 parts of humic acid be uniformly mixed, then add 8~10 parts of magnesium stearates, 8~12 parts of tributyl phosphates, 4~
7 parts of coupling agents, 4~8 parts of dispersing agents are uniformly mixed and obtain composite water treatment medicament.
As a further explanation of the present invention, the initiator is the group of benzoyl peroxide and n,N-Dimethylaniline
It closes.
As a further explanation of the present invention, the crosslinking agent is n-hydroxysuccinimide, diisocyanate, penta 2
One of aldehyde.
As a further explanation of the present invention, the coupling agent is epoxy silane class coupling agent.
As a further explanation of the present invention, the dispersing agent is calgon, sodium tripolyphosphate, dodecyl sulphur
The combination of one or more of sour sodium.
The technical principle that the present invention realizes is:
Present invention FeCl3·6H2O and FeSO4·7H2O prepares MODIFIED Fe3O4Particle, Fe3O4Particle passes through poly- second two
Alcohol is modified to can reduce Fe3O4The surface of magnetic-particle can improve dispersibility, prevent Fe3O4Particle is because close to each other lead
It causes to reunite, improves it and adsorb heavy metal energy, while polyethylene glycol can promote Fe3O4The phase between the other components in raw material
Dissolubility improves the stability of composite water treatment medicament；Under the action of initiator and crosslinking agent, by polyglutamic acid, starch, silicic acid
Sodium and Fe3O4Particle progress is compound, can improve polyglutamic acid swelling ratio after compound, improve the mechanical performance of complex microsphere；It forms sediment
Powder can be improved magnetic composite microsphere dispersibility and rigidity, increase magnetic composite microsphere surface area, improves it and adsorbs heavy metal energy
Power；Sodium metasilicate and Fe3O4Particle can form polysilicon acid molysite, can be improved the stability of magnetic composite microsphere, improve adsorption energy
Power accelerates sinking speed.Diatomite and bagasse are subjected to high-temperature activation in the present invention, so that the hole of diatomite and sugarcane waste residue
Gap becomes finer and close solid, and structure is survivable, improves its adsorption capacity；The tributyl phosphate of addition can extract metal
It takes, is conducive to the separation of heavy metal in waste water, to promote suction-operated of the composite water treatment medicament to heavy metal；Stearic acid
Magnesium, coupling agent and dispersing agent can promote diatomite, sugarcane waste residue, humic acid etc. to carry out compound, enhancing with magnetic composite microsphere
The absorption heavy metal ability of the composite water treatment medicament of preparation reduces its usage amount, improves treatment effeciency.The present invention will be a variety of right
It is compound that there is heavy metal the component of adsorption capacity to carry out, through the compound one-component that can improve present in the heavy metal adsorption
Defect improves it and adsorbs heavy metal ability, can accelerate composite water treatment medicament pair under the synergistic effect between each component
The adsorption and sedimentation speed of heavy metal in waste water, effectively reduces the usage amount of composite water treatment medicament.
The present invention has following good result:
1. the present invention by by the ingredients such as magnetic composite microsphere and humic acid, bagasse progress it is compound after can be improved it is compound
The stability of water treatment agent enhances its adsorption capacity to heavy metal, reduces usage amount, while the recycling of sugarcane waste residue can
To reduce the amount that sugarcane waste residue is discarded, be conducive to improve its use value.
2. the composite water treatment medicament stability for heavy metal containing wastewater treatment that the present invention is prepared is good, operation letter is used
Single, condition is easily controllable, and dosing is small, and sinking speed is fast, and adsorption-flocculation ability is strong, can effectively remove the huge sum of money in waste water
Belong to substance, application value with higher.
3. the composite water treatment medicament that the present invention is prepared is used for heavy metal containing wastewater treatment, wherein Cu2+Removal rate is
98.632~99.579%, Cd2+Removal rate is 98.883~99.441%, Hg2+Removal rate is 97.872~100%, Pb2+It goes
Except rate is 98.455~99150%, Ag+Removal rate is 98.118~99.462%, Cr6+Removal rate be 98.432~
99.558%, Cr3+Removal rate is 98.381~99.460%, Ni2+Removal rate is 98.634~99.532%, and the present invention is compound
Each component cooperates in water treatment agent, mutually promotes, can effectively remove the Cu in waste water2+、Cd2+、Hg2+、Pb2+Deng
Heavy metal.
Specific embodiment
A kind of composite water treatment medicament and its system for heavy metal containing wastewater treatment of the description present invention with reference to embodiments
Preparation Method, these descriptions are not to be further limited to the content of present invention.
Embodiment 1:
A kind of composite water treatment medicament for heavy metal containing wastewater treatment, each constituent of composite water treatment medicament raw material
And its weight fraction ratio are as follows: 25 parts of polyglutamic acids, 22 parts of starch, 12 parts of FeCl3·6H2O, 12 parts of FeSO4·7H2O, 20 parts of silicon
Sour sodium, 18 parts of humic acid, 12 parts of diatomite, 8 parts of magnesium stearates, 10 parts of sugarcane waste residues, 30 parts of polyethylene glycol 200s, 8 parts of tricresyl phosphates
Butyl ester.
A method of preparing the composite water treatment medicament for heavy metal containing wastewater treatment, comprising the following steps:
Step 1) MODIFIED Fe3O4Particle preparation: 12 parts of FeCl are taken3·6H2O, 12 parts of FeSO4·7H2O is dissolved in 25 parts of steamings
In distilled water, 6min is stirred under conditions of stirring rate is 30r/min, 30 parts of polyethylene glycol 200s are then added, in nitrogen protection
The lower prepared 2molL of fast drop-1NaOH solution adjusting pH to 9, is then 60 DEG C in temperature and mixing speed is 800r/
Water bath with thermostatic control 60min cools the temperature to room temperature under the conditions of min, answers product to precipitate reactant with magnet, with distilled water and anhydrous
Ethyl alcohol washs several times repeatedly, and 5h is dried in vacuo at 40 DEG C and obtains MODIFIED Fe3O4Particle；
Step 2) magnetic composite microsphere preparation: take 25 parts of polyglutamic acids, 22 parts of starch, 20 parts of sodium metasilicate to be placed in reaction
In kettle, 50 parts of distilled water are then added and stir 4min under the conditions of stirring rate is 60r/min, add 12 parts of sodium hydroxides, 5
Part initiator being made of benzoyl peroxide and n,N-Dimethylaniline, 6 parts of n-hydroxysuccinimide crosslinking agents stirrings are mixed
Close the MODIFIED Fe obtained with rear addition step 13O4Particle, it is anti-under the conditions of temperature is 120 DEG C and stirring rate is 60r/min
It after answering 4h, then successively washed with water, dehydrated alcohol, filtered, be finally dried under vacuum under the conditions of 50 DEG C after constant weight with magnet point
From, collect and obtain magnetic composite microsphere；
Step 3) composite water treatment medicament preparation: take 12 parts of diatomite, 10 parts of sugarcane waste residues to carry out uniformly mixed be placed on
In high temperature furnace, activation 60min is carried out at 300 DEG C, setting warming temperature is set as 6 DEG C/min, takes out activator mixture material；Then
Activator mixture material is taken out to be cooled to room temperature；The magnetic composite microsphere and activator mixture after cooling for taking step 2 to be prepared
Material, 18 parts of humic acid are uniformly mixed, and it is even then to add 8 parts of magnesium stearates, 8 parts of tributyl phosphates, 4 parts of epoxy silane classes
Connection agent, 4 parts of calgon dispersing agents are uniformly mixed and obtain composite water treatment medicament.
Embodiment 2:
A kind of composite water treatment medicament for heavy metal containing wastewater treatment, each constituent of composite water treatment medicament raw material
And its weight fraction ratio are as follows: 30 parts of polyglutamic acids, 30 parts of starch, 18 parts of FeCl3·6H2O, 18 parts of FeSO4·7H2O, 26 parts of silicon
Sour sodium, 20 parts of humic acid, 16 parts of diatomite, 10 parts of magnesium stearates, 16 parts of sugarcane waste residues, 35 parts of polyethylene glycol 400s, 12 parts of phosphoric acid
Tributyl.
A method of preparing the composite water treatment medicament for heavy metal containing wastewater treatment, comprising the following steps:
Step 1) MODIFIED Fe3O4Particle preparation: 18 parts of FeCl are taken3·6H2O, 18 parts of FeSO4·7H2O is dissolved in 40 parts of steamings
In distilled water, 8min is stirred under conditions of stirring rate is 40r/min, 35 parts of polyethylene glycol 400s are then added, in nitrogen protection
The lower prepared 2molL of fast drop-1NaOH solution adjusts pH to 9, then temperature be 60 DEG C and mixing speed be 800~
Water bath with thermostatic control 60min cools the temperature to room temperature under the conditions of 850r/min, answers product to precipitate reactant with magnet, with distilled water and
Dehydrated alcohol washs several times repeatedly, and 6h is dried in vacuo at 50 DEG C and obtains MODIFIED Fe3O4Particle；
Step 2) magnetic composite microsphere preparation: take 30 parts of polyglutamic acids, 30 parts of starch, 26 parts of sodium metasilicate to be placed in reaction kettle
In, 60 parts of distilled water are then added and stir 6min under the conditions of stirring rate is 80r/min, add 14 parts of sodium hydroxides, 8 parts
Initiator, the 8 parts of diisocyanate cross-linking agents of benzoyl peroxide and n,N-Dimethylaniline composition are stirred equal and add afterwards
Enter the MODIFIED Fe that step 1 obtains3O4Particle reacts 4.5h under the conditions of temperature is 130 DEG C and stirring rate is 60~80r/min
Afterwards, then with water, dehydrated alcohol it successively washs, filter, be finally dried under vacuum to after constant weight with magnet separation, receive under the conditions of 60 DEG C
Collection obtains magnetic composite microsphere；
Step 3) composite water treatment medicament preparation: take 16 parts of diatomite, 16 parts of sugarcane waste residues to carry out uniformly mixed be placed on
In high temperature furnace, activation 90min is carried out at 500 DEG C, setting warming temperature is set as 6 DEG C/min, takes out activator mixture material；Then
Activator mixture material is taken out to be cooled to room temperature；The magnetic composite microsphere and activator mixture after cooling for taking step 2 to be prepared
Material, 20 parts of humic acid are uniformly mixed, and then add 10 parts of magnesium stearates, 12 parts of tributyl phosphates, 7 parts of epoxy silane classes
Coupling agent, 8 parts of sodium tripolyphosphate dispersing agents are uniformly mixed and obtain composite water treatment medicament.
Embodiment 3:
A kind of composite water treatment medicament for heavy metal containing wastewater treatment, each constituent of composite water treatment medicament raw material
And its weight fraction ratio are as follows: 28 parts of polyglutamic acids, 28 parts of starch, 17 parts of FeCl3·6H2O, 15 parts of FeSO4·7H2O, 22 parts of silicon
Sour sodium, 19 parts of humic acid, 14 parts of diatomite, 9.5 parts of magnesium stearates, 12 parts of sugarcane waste residues, 32 parts of cetomacrogol 1000s, 10 parts of phosphorus
Sour tributyl.
A method of preparing the composite water treatment medicament for heavy metal containing wastewater treatment, comprising the following steps:
Step 1) MODIFIED Fe3O4Particle preparation: 17 parts of FeCl are taken3·6H2O, 15 parts of FeSO4·7H2O is dissolved in 30 parts of steamings
In distilled water, 7min is stirred under conditions of stirring rate is 32r/min, 32 parts of cetomacrogol 1000s are then added, is protected in nitrogen
Protect the lower prepared 2molL of fast drop-1NaOH solution adjusts pH to 9, is then 60 DEG C in temperature and is with mixing speed
Water bath with thermostatic control 60min cools the temperature to room temperature under the conditions of 830r/min, answers product to precipitate reactant with magnet, with distilled water and
Dehydrated alcohol washs several times repeatedly, and 5h is dried in vacuo at 42 DEG C and obtains MODIFIED Fe3O4Particle；
Step 2) magnetic composite microsphere preparation: take 28 parts of polyglutamic acids, 28 parts of starch, 22 parts of sodium metasilicate to be placed in reaction
In kettle, 58 parts of distilled water are then added and stir 6min under the conditions of stirring rate is 70r/min, add 13 parts of sodium hydroxides, 6
The initiator that is made of benzoyl peroxide and n,N-Dimethylaniline of part, 6.5 parts of glutaraldehyde cross-linking agent are stirred with after
The MODIFIED Fe that step 1 obtains is added3O4Particle reacts 4.3h under the conditions of temperature is 125 DEG C and stirring rate is 75r/min
Afterwards, then with water, dehydrated alcohol it successively washs, filter, be finally dried under vacuum to after constant weight with magnet separation, receive under the conditions of 58 DEG C
Collection obtains magnetic composite microsphere；
Step 3) composite water treatment medicament preparation: take 14 parts of diatomite, 12 parts of sugarcane waste residues to carry out uniformly mixed be placed on
In high temperature furnace, activation 70min is carried out at 400 DEG C, setting warming temperature is set as 6 DEG C/min, takes out activator mixture material；Then
Activator mixture material is taken out to be cooled to room temperature；The magnetic composite microsphere and activator mixture after cooling for taking step 2 to be prepared
Material, 19 parts of humic acid are uniformly mixed, and then add 9.5 parts of magnesium stearates, 10 parts of tributyl phosphates, 5 parts of epoxy silanes
Class coupling agent, 7 parts of dodecyl sodium sulfate dispersing agents are uniformly mixed and obtain composite water treatment medicament.
Embodiment 4:
A kind of composite water treatment medicament for heavy metal containing wastewater treatment, each constituent of composite water treatment medicament raw material
And its weight fraction ratio are as follows: 27 parts of polyglutamic acids, 26 parts of starch, 15 parts of FeCl3·6H2O, 14 parts of FeSO4·7H2O, 23.5 parts
Sodium metasilicate, 18.5 parts of humic acid, 15 parts of diatomite, 8.5 parts of magnesium stearates, 15 parts of sugarcane waste residues, 31 parts of polyethylene glycol 1500s, 9
Part tributyl phosphate.
A method of preparing the composite water treatment medicament for heavy metal containing wastewater treatment, comprising the following steps:
Step 1) MODIFIED Fe3O4Particle preparation: 15 parts of FeCl are taken3·6H2O, 14 parts of FeSO4·7H2O is dissolved in 35 parts of steamings
In distilled water, 6min is stirred under conditions of stirring rate is 36r/min, 31 parts of polyethylene glycol 1500s are then added, is protected in nitrogen
Protect the lower prepared 2molL of fast drop-1NaOH solution adjusts pH to 9, is then 60 DEG C in temperature and is with mixing speed
Water bath with thermostatic control 60min cools the temperature to room temperature under the conditions of 820r/min, answers product to precipitate reactant with magnet, with distilled water and
Dehydrated alcohol washs several times repeatedly, and 5.5h is dried in vacuo at 48 DEG C and obtains MODIFIED Fe3O4Particle；
Step 2) magnetic composite microsphere preparation: take 27 parts of polyglutamic acids, 26 parts of starch, 23.5 parts of sodium metasilicate to be placed in instead
It answers in kettle, 52 parts of distilled water is then added and stir 5min under the conditions of stirring rate is 75r/min, add 12.5 parts of hydroxides
Sodium, 7 parts of initiators being made of benzoyl peroxide and n,N-Dimethylaniline, 7.5 parts of n-hydroxysuccinimide crosslinking agents
It is stirred the equal MODIFIED Fe obtained with rear addition step 13O4Particle, in temperature be 120 DEG C and stirring rate is 65r/min item
It after reacting 4.2h under part, then successively washed with water, dehydrated alcohol, filtered, after being finally dried under vacuum to constant weight under the conditions of 53 DEG C
Magnetic composite microsphere is obtained with magnet separation, collection；
Step 3) composite water treatment medicament preparation: take 15 parts of diatomite, 15 parts of sugarcane waste residues to carry out uniformly mixed be placed on
In high temperature furnace, activation 85min is carried out at 350 DEG C, setting warming temperature is set as 6 DEG C/min, takes out activator mixture material；Then
Activator mixture material is taken out to be cooled to room temperature；The magnetic composite microsphere and activator mixture after cooling for taking step 2 to be prepared
Material, 18.5 parts of humic acid are uniformly mixed, and then add 8.5 parts of magnesium stearates, 9 parts of tributyl phosphates, 7 parts of epoxy silanes
Class coupling agent, 6 parts be uniformly mixed by the dispersing agent that calgon and sodium tripolyphosphate form obtain Compound Water processing
Medicament.
Embodiment 5:
A kind of composite water treatment medicament for heavy metal containing wastewater treatment, each constituent of composite water treatment medicament raw material
And its weight fraction ratio are as follows: 26 parts of polyglutamic acids, 24 parts of starch, 13 parts of FeCl3·6H2O, 16 parts of FeSO4·7H2O, 24 parts of silicon
Sour sodium, 19.5 parts of humic acid, 13 parts of diatomite, 9 parts of magnesium stearates, 14 parts of sugarcane waste residues, 34 parts of polyethylene glycol, 11 parts of tricresyl phosphates
Butyl ester.
A method of preparing the composite water treatment medicament for heavy metal containing wastewater treatment, comprising the following steps:
Step 1) MODIFIED Fe3O4Particle preparation: 13 parts of FeCl are taken3·6H2O, 16 parts of FeSO4·7H2O is dissolved in 28 parts of steamings
In distilled water, 8min is stirred under conditions of stirring rate is 38r/min, 30~35 parts of polyethylene glycol are then added, is protected in nitrogen
Protect the lower prepared 2molL of fast drop-1NaOH solution adjusts pH to 9, is then 60 DEG C in temperature and is with mixing speed
Water bath with thermostatic control 60min cools the temperature to room temperature under the conditions of 840r/min, answers product to precipitate reactant with magnet, with distilled water and
Dehydrated alcohol washs several times repeatedly, and 6h is dried in vacuo at 45 DEG C and obtains MODIFIED Fe3O4Particle；
Step 2) magnetic composite microsphere preparation: take 26 parts of polyglutamic acids, 24 parts of starch, 24 parts of sodium metasilicate to be placed in reaction
In kettle, 55 parts of distilled water are then added and stir 5.5min under the conditions of stirring rate is 65r/min, add 13.5 parts of hydroxides
Sodium, 7.5 parts of initiators being made of benzoyl peroxide and n,N-Dimethylaniline, 7 parts of glutaraldehyde cross-linking agent are stirred
The MODIFIED Fe obtained with rear addition step 13O4Particle reacts under the conditions of temperature is 130 DEG C and stirring rate is 70r/min
It after 4.1h, then successively washed with water, dehydrated alcohol, filtered, be finally dried under vacuum under the conditions of 58 DEG C after constant weight with magnet point
From, collect and obtain magnetic composite microsphere；
Step 3) composite water treatment medicament preparation: take 13 parts of diatomite, 14 parts of sugarcane waste residues to carry out uniformly mixed be placed on
In high temperature furnace, activation 75min is carried out at 450 DEG C, setting warming temperature is set as 6 DEG C/min, takes out activator mixture material；Then
Activator mixture material is taken out to be cooled to room temperature；The magnetic composite microsphere and activator mixture after cooling for taking step 2 to be prepared
Material, 18~20 parts of humic acid are uniformly mixed, and then add 9 parts of magnesium stearates, 11 parts of tributyl phosphates, 6 parts of epoxy silicon
Alkanes coupling agent, 5 parts be uniformly mixed by the dispersing agent that sodium tripolyphosphate and dodecyl sodium sulfate form obtain it is compound
Water treatment agent.
In order to verify the performance for the composite water treatment medicament that the present invention is prepared, the embodiment of the present invention 1~5 is prepared into
The composite water treatment medicament arrived is used for heavy metal containing wastewater treatment, while using commercially available similar composite water treatment medicament as comparative example pair
Heavy metal containing wastewater treatment, test case are as shown in the table:
1 composite water treatment medicament of table handles heavy metal wastewater thereby situation
The above embodiment of the present invention scheme is only the description of the invention and cannot limit the present invention, is pointed out in claim
Product of the present invention constituent, component ratio, the range of preparation method parameter, and above-mentioned explanation does not point out ginseng of the present invention
Therefore several ranges any change within the meaning and scope equivalent to the claims of the present invention, is all considered to be
It is included within the scope of the claims.
The present invention is and to pass through creative labor by multidigit heavy metal containing wastewater treatment technical staff's long-term work experience accumulation
It moves creation and goes out, the composite water treatment medicament stability for heavy metal containing wastewater treatment that the present invention is prepared is good, uses operation
Simply, condition is easily controllable, and dosing is small, and sinking speed is fast, and flocculation ability is strong, can effectively remove the heavy metal in waste water
Substance, application value with higher.
Claims (7)
1. a kind of composite water treatment medicament for heavy metal containing wastewater treatment, which is characterized in that the composite water treatment medicament raw material
Each constituent and its weight fraction ratio are as follows: 25 ~ 30 parts of polyglutamic acids, 22 ~ 30 parts of starch, 12 ~ 18 parts of FeCl3·6H2O、12~
18 parts of FeSO4·7H2O, 20 ~ 26 parts of sodium metasilicate, 18 ~ 20 parts of humic acid, 12 ~ 16 parts of diatomite, 8 ~ 10 parts of magnesium stearates, 10 ~ 16
Part sugarcane waste residue, 30 ~ 35 parts of polyethylene glycol, 8 ~ 12 parts of tributyl phosphates.
2. being used for the composite water treatment medicament of heavy metal containing wastewater treatment as described in claim 1, which is characterized in that described is poly-
Ethylene glycol is one or more of polyethylene glycol 200, polyethylene glycol 400, cetomacrogol 1000, polyethylene glycol 1500
Combination.
3. a kind of method for preparing the composite water treatment medicament as described in claim 1 for heavy metal containing wastewater treatment, special
Sign is, comprising the following steps:
Step 1) MODIFIED Fe3O4Particle preparation: 12 ~ 18 parts of FeCl are taken3·6H2O, 12 ~ 18 parts of FeSO4·7H2O is dissolved in 25 ~ 40
In part distilled water, 6 ~ 8min is stirred under conditions of stirring rate is 30 ~ 40r/min, and 30 ~ 35 parts of polyethylene glycol are then added,
The prepared 2molL of fast drop under nitrogen protection-1NaOH solution adjusts pH to 9, is then 60 DEG C and stirring in temperature
Water bath with thermostatic control 60min cools the temperature to room temperature under the conditions of speed is 800 ~ 850r/min, answers product to precipitate reactant with magnet,
It is washed repeatedly several times with distilled water and dehydrated alcohol, 5 ~ 6h is dried in vacuo at 40 ~ 50 DEG C and obtains MODIFIED Fe3O4Particle；
Step 2) magnetic composite microsphere preparation: take 25 ~ 30 parts of polyglutamic acids, 22 ~ 30 parts of starch, 20 ~ 26 parts of sodium metasilicate to be placed in
In reaction kettle, 50 ~ 60 parts of distilled water are then added and stir 4 ~ 6min under the conditions of stirring rate is 60 ~ 80r/min, add 12
~ 14 parts of sodium hydroxides, 5 ~ 8 parts of initiators, 6 ~ 8 parts of crosslinking agents are stirred the equal MODIFIED Fe obtained with rear addition step 13O4Grain
Son, after reacting 4 ~ 4.5h under the conditions of temperature is 120 ~ 130 DEG C and stirring rate be 60 ~ 80r/min, then with water, dehydrated alcohol
Successively washing, suction filtration are finally dried under vacuum to after constant weight under the conditions of 50 ~ 60 DEG C and obtain magnetism again with magnet separation, collection
Close microballoon；
Step 3) composite water treatment medicament preparation: take 12 ~ 16 parts of diatomite, 10 ~ 16 parts of sugarcane waste residues to carry out being uniformly mixed postposition
In high temperature furnace, 60 ~ 90min of activation is carried out at 300 ~ 500 DEG C, setting warming temperature is set as 6 DEG C/min, then takes out activation
Mixed material is cooled to room temperature；The magnetic composite microsphere and activator mixture material after cooling, 18 ~ 20 for taking step 2 to be prepared
Part humic acid is uniformly mixed, then add 8 ~ 10 parts of magnesium stearates, 8 ~ 12 parts of tributyl phosphates, 4 ~ 7 parts of coupling agents, 4 ~
8 parts of dispersing agents are uniformly mixed and obtain composite water treatment medicament.
4. a kind of method of the composite water treatment medicament for heavy metal containing wastewater treatment as claimed in claim 3, feature exist
In the initiator is the combination of benzoyl peroxide and n,N-Dimethylaniline.
5. a kind of method of the composite water treatment medicament for heavy metal containing wastewater treatment as claimed in claim 3, feature exist
In the crosslinking agent is one of n-hydroxysuccinimide, diisocyanate, glutaraldehyde.
6. a kind of method of the composite water treatment medicament for heavy metal containing wastewater treatment as claimed in claim 3, feature exist
In the coupling agent is epoxy silane class coupling agent.
7. a kind of method of the composite water treatment medicament for heavy metal containing wastewater treatment as claimed in claim 3, feature exist
In the dispersing agent is the group of one or more of calgon, sodium tripolyphosphate, dodecyl sodium sulfate
It closes.
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